X-ray Photoelectron Spectroscopy Investigation Research Articles

Study of the electronic structure of Ce0.95Fe0.05O2-δ thin film using X-ray photoelectron spectroscopy

In the present work, the effect of the oxygen partial pressure (OPP) has been studied on the electronic structure of the Ce0.95Fe0.05O2-δ thin film (TF) through Raman spectroscopy, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The varying OPP, from 200 mTorr to 1 mTorr, was observed to vary the oxidation conditions during TF deposition. The oxygen valency was estimated to be reduced along with the generation of oxygen vacancies as determined via Raman analysis. The AFM analysis revealed the lowered values of the roughness parameters which indicated that reduction in OPP is associated with the smoothness of the film surface. The film surface was found to be reduced, as characterized by XPS investigation, as a result of the change in valency of Ce from +4 to +3 due to reduced OPP. The concentration of Ce3+ state was estimated to increase from 19.5% to 33% with reducing OPP. This evidently supports the formation of oxygen vacancies since the reduction of the valence state of Ce is known to be accompanied by the generation of oxygen vacancies. The O1 s spectra confirmed the oxygen non-stoichiometry as a function of OPP, whereas, Fe 2p suggested the mixed-valence state of Fe (Fe2+/Fe3+) in Ce0.95Fe0.05O2-δ (TF). To put in brief, the variation in OPP affects the chemical composition of the material by modifying its electronic structure via controlling the exchange interactions in the core structure of the compound.

Effects of Surface Heterogeneity of α-Quartz and α-Cristobalite on Adsorption of Crystal Violet

Silica minerals are a kind of important minerals and widespread on the earth’s surface. They play an irreplaceable role in the whole geochemistry and environment processes. The diversity in the crystal structure of SiO2 polymorphs might lead to the heterogeneity in their surface microstructures and properties. As two common SiO2 polymorph minerals in soil and sediments, α-quartz and α-cristobalite have been studied for the effects of their surface heterogeneity on adsorption behaviors toward crystal violet (CV) by batch adsorption experiments in different specific surface areas (SSAs) and at different pH values and temperatures, as well as by X-ray photoelectron spectroscopy (XPS) investigation. Owing to the larger surface site density, the saturated adsorption amount of α-quartz was larger than that of α-cristobalite. It was also indicated by the larger slope of adsorption lines as a function of SSA. The adsorption capacity of both increased with increasing pH and temperature. In the thermodynamic study, the negative ΔG indicated that the adsorption of CV on the surface was spontaneous and the positive ΔH suggested that the reaction was endothermic. The well-fitted Langmuir adsorption isotherms suggested that the CV adsorption was monolayer adsorption. The adsorption interaction force was mainly involved in electrostatic attraction force between the negatively charged surface reactive sites and positively charged N atoms in the dimethylamino groups of CV. The XPS spectra of N 1s showed that the stoichiometric ratio of Nlow/Nhigh changed from lower than 2:1 to about 2:1 as the adsorption changed from the unsaturated to saturated state. The change reflected that the spatial arrangement of adsorbed CV monomer on the mineral surface could be readjusted by lifting the average tilt angle between the average plane of the CV monomer and the sample surface during the adsorption process. Surface heterogeneity of α-quartz and α-cristobalite controlled the different distributions and postures of adsorbed CV monomers on the surface. The CV monomers adsorbed on α-quartz presented a larger average tilt angle because of its larger surface reactive site density, while α-cristobalite did conversely.

Novel yellow light emission from vanadyl ions-doped calcium-lithium hydroxyapatite nanopowders: structural, optical, and photoluminescence properties

Phosphor luminescent materials, especially those activated with transition metal ions, have been extensively investigated during the last decade because of their potential in various applications such as displays, medical imaging, lighting, and fluorescent lamps. In this study, a mechanochemical approach was used for the synthesis of novel yellow light-emitting vanadyl ion (VO2+)-doped calcium-lithium hydroxyapatite (CLHA) nanophosphors. The structural, morphological, optical, photoluminescence, and chromaticity properties of the as-prepared nanopowders were systematically examined. Phase structural analysis showed that the as-prepared samples were highly crystalline and corresponded to the hexagonal crystal phase of hydroxyapatite. X-ray photoelectron spectroscopy investigation indicated the existence of elements. The spectroscopic results indicate that the doped VO2+ ions belong to the tetragonally distorted octahedral site symmetry. The chromaticity results show that the chromaticity coordinates (x, y) for the VO2+-doped CLHA nanopowders were (0.448, 0.401), (0.430, 0.384), and (0.423, 0.377). The emission colors are positioned in the orange, orange-yellow, and pale-yellow regions, respectively, for VO2+-doped CLHA nanopowders. Thus, the light emission properties shift from orange to yellow as the dopant concentration increases from 0.01 to 0.05 mol%. These results demonstrate that phosphor materials doped with transition metal ions are suitable for display device applications.

Heterometallic Clusters with Multiple Rare Earth Metal-Transition Metal Bonding.

Although a series of complexes with rare earth (RE) metal-metal bonds have been reported, complexes which have multiple RE-Rh bonds are unknown. Here we present the identification of the first example of a molecule containing multiple RE-Rh bonds. The complex with multiple Ce-Rh bonds was synthesized by the reduction of a d-f heterometallic molecular cluster Ce{N[(CH2CH2NPiPr2)RhCl(COD)]3} with excess potassium-graphite. The oxidation state of Ce in 3a appears to be a mixture of Ce(III) and Ce(IV), which was confirmed by X-ray photoelectron spectroscopy, magnetism, and theoretical investigations (DFT and CASSCF). For comparison, the analogous species with multiple La(III)-Rh and Nd(III)-Rh bonds were also constructed. This study provides a possible route for the construction of complexes with multiple RE metal-metal bonds and an investigation of their potential properties and applications.

In situ XPS investigation of the X-ray-triggered decomposition of perovskites in ultrahigh vacuum condition

X-ray photoelectron spectroscopy (XPS) has been used to investigate the composition of perovskite films upon exposure to different environmental factors, such as moisture, heat, and UV light. However, few research studies have determined that the X-ray itself could cause damage to the perovskite crystals. In this study, the X-ray-induced degradation of CH3NH3PbI3 perovskite films was investigated via XPS within an in situ ultrahigh vacuum system. It is demonstrated that fresh methylammonium lead iodine contains Pb2+ without the initial existence of Pb0. The Pb0 signal was discovered after a few hours of soft X-ray exposure, which indicates that the CH3NH3PbI3 perovskite structure undergoes a decomposition process to form metallic Pb. In addition, the nitrogen content was found to be significantly decreasing in the first hour of X-ray exposure. The discovery of the X-ray-induced chemical state change and the volatile methylamine of perovskite crystals could be further applied as an indicator for the field of X-ray sensors or detectors.

Thermally Stimulated Wettability Transformations on One-Cycle Atomic Layer Deposition-Coated Cellulosic Paper: Applications for Droplet Manipulation and Heat Patterned Paper Fluidics.

Cellulosic materials are widely used in daily life for paper products and clothing as well as for emerging applications in sustainable packaging and inexpensive medical diagnostics. Cellulose has a high density of hydroxyl groups that create strong intra- and interfiber hydrogen bonding. These abundant hydroxyl groups also make cellulose superhydrophilic. Schemes for hydrophobization and spatially selective hydrophobization of cellulosic materials can expand the application space for cellulose. Cellulose is often hydrophobized through wet chemistry surface modification methods. This work reports a new modification method using a combination of atomic layer deposition (ALD) and atmospheric heating to alter the wettability of purely cellulosic chromatography paper. We find that once the cellulosic paper is coated with a single ALD cycle (1cy-ALD) of Al2O3, it can be made sticky superhydrophobic after a 150 °C ambient post-ALD heating step. An X-ray photoelectron spectroscopy investigation reveals that the ALD-modified cellulosic surface becomes more susceptible to adsorption of adventitious carbon upon heating than an untreated cellulosic surface. This conclusion is further supported by the ability to use alternating air plasma and heat treatments to reversibly transition between the hydrophilic and hydrophobic states. We attribute the apparent abruptness of this wetting transition to a Cassie-Wenzel-like phenomenon, which is also consistent with the sticky hydrophobic wetting behavior. Using scanning probe methods, we show that the surfaces have roughness at multiple length scales. Using a Cassie-Wenzel model, we show how a small change in the surface's Young's contact angle-upon adsorption of adventitious carbon-can lead to an abrupt increase in hydrophobicity for surfaces with such roughnesses. Finally, we demonstrate the ability to spatially pattern the wettability on these 1cy-ALD-treated cellulosic papers via selective heating. This ALD-treated hydrophobic paper also shows promise for microliter droplet manipulation and patterned lab-on-paper devices.

Insights into the adsorption mechanism of tannic acid by a green synthesized nano-hydroxyapatite and its effect on aqueous Cu(II) removal.

The polyphenolic tannic acid (TA) has been widely used in the stabilization and surface modification of nanomaterials. The interaction mechanism of TA with the biogenic nano-hydroxyapatite (nHAP) and its environmental importance, however, are poorly understood. This study explored the adsorption of TA using the green synthesized, eggshell-derived nHAP and implications of this process for the removal of aqueous Cu(II) via batch adsorption experiments, Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) investigations. TA adsorption by nHAP was a complex pH-dependent process and significantly correlated with TA molecule speciation and amphoteric properties of nHAP via multiple adsorption modes including surface complexation, electrostatic attraction, and hydrogen bond. The maximum TA adsorption amount was found to be 94.8mg/g for less crystalline nHAP with lower calcination temperature. In the ternary Cu-TA-nHAP systems, TA promoted Cu(II) adsorption at pH<5 and reduced Cu(II) uptake at pH>5. Further studies of the effects of ionic strength and addition sequences, as well as Raman, FTIR, and XPS analyses revealed Cu(II) adsorption on nHAP was mainly dominated by inner-sphere surface complexation. These results can shed light on not only the utility of biogenic nHAP for TA and Cu(II) adsorption but also the evaluation of the effect of TA on the environmental behavior of heavy metals.

Influence of Conditioning Temperature on Defects in the Double Al2O3/ZnO Layer Deposited by the ALD Method.

In this work, we present the results of defects analysis concerning ZnO and Al2O3 layers deposited by atomic layer deposition (ALD) technique. The analysis was performed by the X-band electron paramagnetic resonance (EPR) spectroscopy, transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) methods. The layers were either tested as-deposited or after 30 min heating at 300 °C and 450 °C in Ar atmosphere. TEM and XPS investigations revealed amorphous nature and non-stoichiometry of aluminum oxide even after additional high-temperature treatment. EPR confirmed high number of defect states in Al2O3. For ZnO, we found the as-deposited layer shows ultrafine grains that start to grow when high temperature is applied and that their crystallinity is also improved, resulting in good agreement with XPS results which indicated lower number of defects on the layer surface.

Polymer-Derived Ceramic Nanoparticle/Edge-Functionalized Graphene Oxide Composites for Lithium-Ion Storage.

Polymer-derived ceramics demonstrate great potential as lithium-ion battery anode materials with good cycling stability and large capacity. SiCNO ceramic nanoparticles are produced by the pyrolysis of polysilazane nanoparticles that are synthesized via an oil-in-oil emulsion crosslinking and used as anode materials. The SiCNO nanoparticles have an average particle size of around 9 nm and contain graphitic carbon and Si3N4 and SiO2 domains. Composite anodes are produced by mixing different concentrations of SiCNO nanoparticles, edge-functionalized graphene oxide, polyvinylidenefluoride, and carbon black Super P. The electrochemical behavior of the anode is investigated to evaluate the Li-ion storage performance of the composite anode and understand the mechanism of Li-ion storage. The lithiation of SiCNO is observed at ∼0.385 V versus Li/Li+. The anode has a large capacity of 705 mA h g-1 after 350 cycles at a current density of 0.1 A g-1 and shows an excellent cyclic stability with a capacity decay of 0.049 mA h g-1 (0.0097%) per cycle. SiCNO nanoparticles provide a large specific area that is beneficial to Li+ storage and cyclic stability. In situ transmission electron microscopy analysis demonstrates that the SiCNO nanoparticles exhibit extraordinary structural stability with 9.36% linear expansion in the lithiation process. The X-ray diffraction and X-ray photoelectron spectroscopy investigation of the working electrode before and after cycling suggests that Li+ was stored through two pathways in SiCNO lithiation: (a) Li-ion intercalation of graphitic carbon in free carbon domains and (b) lithiation of the SiO2 and Si3N4 domains through a two-stage process.

A rechargeable all-solid-state sodium peroxide (Na2O2) battery with low overpotential

Na–O2 batteries have been attracting attention owing to their intrinsically high theoretical energy density. Several Na–O2 systems can produce various discharge products with different electrochemical performances. For example, sodium superoxide (NaO2) batteries have a low overpotential, and sodium peroxide (Na2O2) batteries have a high capacity. Studies of Na2O2 batteries are relatively scarce, owing to the difficulty of forming pure Na2O2 discharge products. A pure Na2O2 battery system is highly desirable for fully exploring the formation and decomposition of Na2O2 in Na–O2 batteries and evaluating their potential. This model of a Na2O2 battery should also be compatible with in situ characterization. To this end, we constructed a simple rechargeable all-solid-state Na2O2 battery. Using a nanoporous gold film as the cathode and Na–β″-Al2O3 as a solid electrolyte, we assembled a Na–O2 battery that can produce and decompose Na2O2. The all-solid-state Na–O2 battery is a simple model for conducting in situ ambient-pressure x-ray photoelectron spectroscopy (APXPS) investigations. The battery can be cycled at a low overpotential (≈450 mV). Qualitative and quantitative analyses of the APXPS and Raman results demonstrated that Na2O2 was the main discharge product and its transformation occurred during the charge and discharge periods. The operando investigation of this type of all-solid-state Na2O2 battery can help in the comprehensive exploration of the potential of Na–O2 batteries.

X-ray Photoelectron Spectroscopy and Resonant X-ray Spectroscopy Investigations of Interactions between Thin Metal Catalyst Films and Amorphous Titanium Dioxide Photoelectrode Protection Layers

The use of electrochemistry, X-ray photoelectron spectroscopy, and resonant X-ray spectroscopy has unlocked the paradox of interfacial hole conduction through amorphous TiO2 (a-TiO2) to deposited N...

Combined XPS and DFT investigation of the adsorption modes of methyl enol ether functionalized cyclooctyne on Si(001).

The reaction of methyl enol ether functionalized cyclooctyne on the silicon (001) surface was investigated by means of X‐ray photoelectron spectroscopy (XPS) and density functional theory (DFT). Three different groups of final states were identified; all of them bind on Si(001) via the strained triple bond of cyclooctyne but they differ in the configuration of the methyl enol ether group. The majority of molecules adsorbs without additional reaction of the enol ether group; the relative contribution of this configuration to the total coverage depends on substrate temperature and coverage. Further configurations include enol ether groups which reacted on the silicon surface either via ether cleavage or enol ether groups which transformed on the surface into a carbonyl group.

CuWO4 with CuO and Cu(OH)2 Native Surface Layers for H2S Detection under in-Field Conditions.

The paper presents the possibility of detecting low H2S concentrations using CuWO4. The applicative challenge was to obtain sensitivity, selectivity, short response time, and full recovery at a low operating temperature under in-field atmosphere, which means variable relative humidity (%RH). Three different chemical synthesis routes were used for obtaining the samples labeled as: CuW1, CuW2, and CuW3. The materials have been fully characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). While CuWO4 is the common main phase with triclinic symmetry, different native layers of CuO and Cu(OH)2 have been identified on top of the surfaces. The differences induced into their structural, morphological, and surface chemistry revealed different degrees of surface hydroxylation. Knowing the poisonous effect of H2S, the sensing properties evaluation allowed the CuW2 selection based on its specific surface recovery upon gas exposure. Simultaneous electrical resistance and work function measurements confirmed the weak influence of moisture over the sensing properties of CuW2, due to the pronounced Cu(OH)2 native surface layer, as shown by XPS investigations. Moreover, the experimental results obtained at 150 °C highlight the linear sensor signal for CuW2 in the range of 1 to 10 ppm H2S concentrations and a pronounced selectivity towards CO, CH4, NH3, SO2, and NO2. Therefore, the applicative potential deserves to be noted. The study has been completed by a theoretical approach aiming to link the experimental findings with the CuW2 intrinsic properties.

Enhanced performance of magnetic montmorillonite nanocomposite as adsorbent for Cu(II) by hydrothermal synthesis

Magnetic montmorillonite nanocomposites of Fe3O4/Mt were synthesized via a hydrothermal method. The syntheses were conducted by dispersing iron oxide precursors (FeSO4 and FeCl3) in montmorillonite in the Fe content range of 10–50 wt%. The properties of the nanocomposites were investigated by X-ray diffraction, gas sorption analysis, scanning electron microscopy-energy dispersive spectroscopy, transmission electron microscopy, and vibration sample magnetometer measurements. The kinetics and isotherms for Cu(II) adsorption by the nanocomposites were evaluated. The results showed that the iron oxide in the nanocomposite was in the form of Fe3O4, with a particle size of 10–60 nm, where the particle size is smaller than that produced by the co-precipitation method. The nanocomposites displayed good Cu(II) adsorption capacity and easy separation owing to the magnetic properties. The kinetics of Cu(II) adsorption followed a pseudo–second–order kinetic model and fit to the Langmuir model, with a maximum uptake of 154.45 mg g−1 over the nanocomposite containing 30 wt%. Fe. The kinetics, FTIR study and X-ray photoelectron spectroscopy investigation revealed that the adsorption mechanism was influenced by the specific surface area, magnetism, and reduction-oxidation mechanism on the surface of the nanocomposite. Furthermore, the nanocomposites demonstrated chemical stability, given that the adsorption capacity was maintained after five cycles.

MoS2 nanorods anchored reduced graphene oxide nanohybrids for electrochemical energy conversion applications

Herein, the hydrothermal route has been explored to design a novel network of molybdenum sulfide (MoS 2 ) nanorods/reduced graphene oxide (rGO) by varying wt% of MoS 2 (10–30 wt%) for the highly stable and efficient electrochemical energy conversion applications involving dye sensitized solar cells (DSSCs); and direct methanol fuel cells (DMFCs). The MoS 2 /rGO nanohybrids network has been systematically characterized by X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). XRD, HRTEM, Raman and XPS investigations confirmed the uniform and homogenous anchoring of MoS 2 nanorods on the rGO sheets in the MoS 2 /rGO nanohybrids. It has been revealed that the wt% of MoS 2 in MoS 2 /rGO nanohybrids strongly affects the anchoring of MoS 2 nanorods on rGO sheets which in turn affects their electrocatalytic behavior. The optimized MoS 2 /rGO nanohybrids with 20 wt% of MoS 2 nanorods exhibited long term stability and highly efficient electrocatalytic behavior. DSSCs assembled with MoS 2 /rGO nanohybrids as CE exhibited comparable power conversion efficiency (PCE) relative to standard DSSC. The optimized anchoring of MoS 2 on rGO sheets resulted in high current density as compared to rGO based electrocatalyst in MORs. Moreover, reproducibility of CV curves revealed high stability of MoS 2 /rGO nanohybrids under harsh electrolyte medium. • Synthesis of novel network of molybdenum sulfide nanorods (MoS 2 )/ reduced graphene oxide (rGO) using hydrothermal method. • Optimized MoS 2 /rGO nanohybrids (20 wt% of MoS 2 ) exhibits long term stability and high electrocatalytic behavior. • MoS 2 /rGO nanohybrids act as effective replacement of Pt electrocatalyst in DSSCs and methanol oxidation reactions in DMFCs.

Towards reliable X-ray photoelectron spectroscopy: Sputter-damage effects in transition metal borides, carbides, nitrides, and oxides

Ar+ sputter etching is often used prior to X-ray photoelectron spectroscopy (XPS) analyses with the intention to remove surface oxides and contaminants. Since the XPS probing depth is comparable to the thickness of the ion-beam modified layer the signal from the latter dominates the spectra. We check here the conditions for reliable XPS analysis by studying ion irradiation effects for single-phase Group IVB transition metal (IVB-TM) boride, carbide, nitride, and oxide thin film specimens. The extent of sputter damage, manifested by changes in the surface composition, binding energy shift, peak broadening, and the appearance of new spectral features, varies greatly between material systems: from subtle effects in the case of IVB-TM carbides to a complete change of spectral components for IVB-TM oxides. The determining factors are: (i) the nature of compounds that may form as a result of ion-induced mixing in the affected layer together with (ii) the final elemental composition after sputtering, and (iii) the thickness of the Ar+-affected layer with respect to the XPS probing depth. Our results reveal that the effects of Ar+ ion irradiation on XPS spectra cannot be a priori neglected and a great deal of scrutiny, if not restraint, is necessary during spectra interpretation.

On the interpretation of X-ray photoelectron spectra of Pt-Cu bimetallic alloys

The progress in the design of a perspective alloy catalyst relies on correct interpretation of its photoelectron spectra. Particularly, X-ray photoelectron spectroscopic (XPS) analysis of platinum-copper alloys represents a serious challenge for both qualitative and quantitative analyses due to the complexity of the Pt 4f spectra arising from its overlapping with the Cu 3p region. Studies regarding XPS investigation of Pt-Cu alloys often ignore the Cu 3p contribution while fitting Pt 4f spectra, which leads to partially incorrect interpretation of measured XPS data. This is most noticeable for alloys containing more than 50 % of platinum where the low-intensity Cu 3p core levels can be hidden under a more intense contribution of Pt 4f. In this work, we present the correct way of processing photoemission spectra of such systems. First, we thoroughly examine the XPS Cu 3p spectra of pure copper surfaces of different oxidation states, namely Cu°, Cu+, and Cu2+. Then, the obtained results are applied for the fitting of Pt 4f spectra of both metallic and oxidized Pt-Cu systems. The precise curve-fitting and data analysis procedure showcased in this study can be utilized to eliminate uncertainties in the analysis of Pt-Cu photoemission spectra.

Degradation phenomena on atmospheric air plasma treatment of polyester fabrics

Surface treatments are commonly employed on woven fabrics to render properties such as dyeability, antibacterial feature, self-cleaning, etc. A variety of environmentally benign cold plasma treatments present a viable alternative to the conventional wet chemical processes. The various plasma designs, however, may differ in the efficiency and the effect they exert on the fabrics. In this work a polyester woven fabric was treated by diffuse co-planar surface barrier discharges in atmospheric air for various lengths of time. X-ray photoelectron spectroscopy investigation revealed that changes in surface chemistry occurred within 30 s of treatment. Carbon containing contaminations were removed and the surface became more oxidized, however, new chemical states have not been developed. As an effect, wettability and wickability of the fabric significantly increased. A slight increase in the roughness also occurred after treatment according to AFM measurements. The tensile strength of the fabric showed a gradually decreasing trend with respect to treatment time that could be attributed to damaged sites in the fabric generated by the local excessive etching of the plasma. The results show the detrimental effect of prolonged plasma treatment on the woven poly(ethylene-terephthalate) (PET) fabrics. Employing longer treatment times of 120 s and 180 s the mechanical properties reduced by ca. 40% and 50%, respectively, without significant changes in the surface morphology.

High-temperature intrinsic ferromagnetism in heavily Fe-doped GaAs layers

The layers of a high-temperature novel GaAs:Fe diluted magnetic semiconductor (DMS) with an average Fe content up to 20 at. % were grown on (001) i-GaAs substrates using a pulsed laser deposition in a vacuum. The transmission electron microscopy (TEM) and energy-dispersive x-ray spectroscopy investigations revealed that the conductive layers obtained at 180 and 200 ºC are epitaxial, do not contain any second-phase inclusions, but contain the Fe-enriched columnar regions of overlapped microtwins. The TEM investigations of the non-conductive layer obtained at 250 ºC revealed the embedded coherent Fe-rich clusters of GaAs:Fe DMS. The x-ray photoelectron spectroscopy investigations showed that Fe atoms form chemical bonds with Ga and As atoms with almost equal probability and thus the comparable number of Fe atoms substitute on Ga and As sites. The n-type conductivity of the obtained conductive GaAs:Fe layers is apparently associated with electron transport in a Fe acceptor impurity band within the GaAs band gap. A hysteretic negative magnetoresistance (MR) was observed in the conductive layers up to room temperature (RT). MR measurements point to the out-of-plane magnetic anisotropy of the conductive GaAs:Fe layers related to the presence of the columnar regions. The studies of the magnetic circular dichroism confirm that the layers obtained at 180, 200 and 250 ºC are intrinsic ferromagnetic semiconductors and the Curie point can reach up to at least RT in case of the conductive layer obtained at 200 ºC. It was suggested that in heavily Fe-doped GaAs layers the ferromagnetism is related to the Zener double exchange between Fe atoms with different valence states via an intermediate As and Ga atom.

Application of macroalgal biomass derived biochar and bioelectrochemical system with Shewanella for the adsorptive removal and biodegradation of toxic azo dye

The present study aimed towards adsorptive removal of the toxic azo dye onto biochar derived from Eucheuma spinosum biomass. Characterization of the produced biochar was performed using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and Brunauer-Emmett-Teller (BET). Eucheuma spinosum biochar (ES-BC) produced at 600 °C revealed a maximum adsorption capacity of 331.97 mg/g towards reactive red 120 dye. The adsorption data fitted best to the pseudo-second order kinetics (R2 > 0.99) and Langmuir isotherm (R2 > 0.98) models. These adsorption models signified the chemisorption mechanism with monolayer coverage of the adsorbent surface with dye molecules. Furthermore, the adsorption process was mainly governed by electrostatic interaction, ion exchange, metal complexation, and hydrogen bonding as supported by the solution pH, FTIR, XPS, and XRD investigation. Nevertheless, alone adsorption technology could not offer a complete solution for eliminating the noxious dyes. Therefore, the bioelectrochemical system (BES) equipped with previously isolated marine Shewanella marisflavi BBL25 was intended for the complete remediation of azo dye. The BES II demonstrated highest dye decolorization (97.06%) within 48 h at biocathode where the reductive cleavage of the azo bond occurred. Cyclic voltammetry (CV) studies of the BES revealed perfect redox reactions taking place where the redox mediators shuttled the electrons to the dye molecule to accelerate the dye decolorization. Besides, the GC-MS analysis revealed biotransformation of the dye into less toxic metabolites as tested using a phyto and cytogenotoxicity.